Fungicidal mixtures of an oxime ether carboxylic acid amide with an N-trichloromethyl thiophtalimide

ABSTRACT

A fungicidal mixture comprising 
     a) an oxime ether carboxamide of the formula I ##STR1##  where R is hydrogen or halogen and b) a phthalimide derivative selected from the group consisting of the compounds II and III ##STR2##  in a synergistically active amount.

This application is a 371 of PCT/EP96/03453, filed Aug. 5, 1996.

The present invention relates to a fungicidal mixture which comprises

a) an oxime ether carboxamide of the formula I ##STR3## where R ishydrogen or halogen and b) a phthalimide derivative selected from thegroup consisting of the compounds II and III ##STR4## in asynergistically active amount.

Moreover, the invention relates to methods of controlling harmful fungiusing mixtures of the compounds I and II or the compounds I and III andto the use of the compound I, the compound II and the compound III forthe preparation of such mixtures.

The compounds of the formula I, their preparation and their actionagainst harmful fungi are disclosed in the literature (WO-A 95/18,789).Also disclosed are the phthalimide derivatives II and III (U.S. Pat.Nos. 2,553,770; 2,553,771; 2,553,776), their preparation and theiraction against harmful fungi.

It was an object of the present invention to provide mixtures which havean improved action against harmful fungi combined with a reduced totalamount of active ingredients applied (synergistic mixtures) with a viewto reducing the rates of application and to improving the spectrum ofaction of the known compounds.

Accordingly, we have found that this object is achieved by the mixturesdefined at the outset. Moreover, we have found that better control ofthe harmful fungi is possible by applying the compound I and thecompound II or the compound III simultaneously together or separately orby applying the compound I and the compounds [sic] II or the compoundIII in succession than when the individual compounds are used.

R in formula I is hydrogen or a halogen atom such as fluorine, chlorine,bromine or iodine, especially hydrogen, fluorine and chlorine, inparticular hydrogen or fluorine.

In relation to the C═N double bond, the compounds of the formula I canbe present in the E or the Z configuration (in relation to thecarboxylic acid function). Accordingly, they can be used in the mixtureaccording to the invention in each case either in the form of the pure Eor Z isomers or else in the form of an E/Z isomer mixture. The E/Zisomer mixture or the E isomer is preferably used, the E isomer beingespecially preferred.

The C═N double bonds of the oxime ether groups in the side chain of thecompounds I can exist in each case in the form of pure E or Z isomers orin the form of E/Z isomer mixtures. The compounds I can be used in themixtures according to the invention as isomer mixtures or else as thepure isomers. With a view to their use, compounds I which areparticularly preferred are those where both oxime ether groups in theside chain are in the E configuration (E/E).

Due to the basic character of the NH group, the compounds I are capableof forming adducts or salts with inorganic or organic acids or withmetal ions.

Examples of inorganic acids are hydrohalic acids such as hydrofluoricacid, hydrochloric acid, hydrobromic acid and hydriodic acid, sulfuricacid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, formic acid, carbonic acid, andalkanoic acids such as acetic acid, trifluoroacetic acid,trichloroacetic acid and propionic acid, and also glycolic acid,thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid,cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids havingstraight-chain or branched alkyl radicals of 1 to 20 carbon atoms),arylsulfonic acids or aryldisulfonic acids (aromatic radicals such asphenyl and naphthyl which have attached to them one or two sulfogroups), alkylphosphonic acids (phosphonic acids having straight-chainor branched alkyl radicals of 1 to 20 carbon atoms), arylphosphonicacids or aryldiphosphonic acids (aromatic radicals such as phenyl andnaphthyl which have attached to them one or two phosphoric acidradicals), it being possible for the alkyl or aryl radicals to haveattached to them further substituents, eg. p-toluenesulfonic acid,salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid,2-acetoxybenzoic acid etc.

Suitable metal ions are, in particular, the ions of the elements of thesecond main group, in particular calcium and magnesium, of the third andfourth main group, in particular aluminum, tin and lead, and of thefirst to eighth sub-group, in particular chromium, manganese, iron,cobalt, nickel, copper, zinc and others. Especially preferred are themetal ions of the elements of the sub-groups of the fourth period. Themetals can exist in the various valencies which they can assume.

When preparing the mixtures, it is preferred to employ the pure activeingredients I and II, or III, with which further active ingredientsagainst harmful fungi or other pests such as insects, arachnids ornematodes, or else herbicidal or growth-regulating active ingredients orfertilizers can be admixed, if so required.

The mixtures of the compounds I and II, or I and III, or thesimultaneous joint or separate use of the compounds I and II, or I andIII, have an outstanding action against a wide spectrum ofphytopathogenic fungi, in particular from the classes of the Ascomycetesand Basidiomycetes. Some of them act systemically and can therefore alsobe employed as foliar- and soil-acting fungicides.

They are especially important for controlling a large number of fungi ina variety of crop plants such as cotton, vegetable species (eg.cucumbers, beans and cucurbits), barley, grass, oats, coffee, maize,fruit species, rice, rye, soya, grape vine, wheat, ornamentals, sugarcane, and a variety of seeds.

They are particularly suitable for controlling the followingphytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals,Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,Podosphaera leucotricha in apples, Puccinia species in cereals,Rhizoctonia species in cotton and lawns, Ustilago species in cereals andsugar cane, Venturia inaequalis (scab) in apples, Helminthosporiumspecies in cereals, Septoria nodorum in wheat, Botrytis cinera [sic](gray mold) in strawberries and grape vines, Cercospora arachidicola ingroundnuts, Pseudocercosporella herpotrichoides in wheat and barley,Pyricularia oryzae in rice, Phytophthora infestans in potatoes andtomatoes, Pseudoperonospora Cubense [sic] in cucurbits, Plasmoparaviticola in grape vines, Alternaria species in vegetables and fruit, andFusarium and Verticillium species.

Furthermore, they can be used in the protection of materials (eg. theprotection of wood), for example against Paecilomyces variotii.

The compounds I and II, or I and III, can be applied simultaneouslytogether or separately or in succession, the order in the case ofseparate application generally not having any effect on the result ofthe control measures.

The compounds I and II, or I and III, are usually used in a weight ratioof 1:1 to 1:100, preferably 1:1 to 1:50, in particular 1:3 to 1:30 (I:IIor III).

The application rates in the mixtures according to the invention arefrom 0.02 to 5 kg/ha, preferably 0.05 to 3.5 kg/ha, in particular 0.1 to3.5 kg/ha, depending on the nature of the desired effect. In the case ofthe compounds I, the application rates are from 0.005 to 0.5 kg/ha,preferably 0.01 to 0.5 kg/ha, in particular 0.01 to 0.3 kg/ha.Correspondingly, the application rates in the case of the compounds II,or the compounds III, are from 0.1 to 5 kg/ha, preferably 0.1 to 3.5kg/ha.

For seed treatment, the application rates of the mixture are generallyfrom 0.001 to 50 g/kg of seed, preferably 0.01 to 10 g/kg, in particular0.01 to 5 g/kg.

If it is phytopathogenic harmful fungi that are to be controlled, theseparate or joint application of the compounds I and II, or I and III,or of the mixtures of the compounds I and II, or I and III, is effectedby spraying or dusting the seeds, the plants or the soils before orafter sowing the plants or before or after plant emergence.

The fungicidal synergistic mixtures according to the invention, or thecompounds I and II, or I and III, can be formulated for example in theform of ready-to-spray solutions, powders and suspensions or in the formof highly concentrated aqueous, oily or other suspensions, dispersions,emulsions, oil dispersions, pastes, dusts, materials for spreading orgranules, and applied by spraying, atomizing, dusting, spreading orpouring. The use form depends on the intended purpose; in any case, itshould guarantee as fine and uniform a distribution as possible of themixture according to the invention.

The formulations are prepared in a manner known per se, eg. by addingsolvents and/or carriers. It is usual to admix inert additives such asemulsifiers or dispersants with the formulations.

Suitable surfactants are the alkali metal salts, alkaline earth metalsalts and ammonium salts of aromatic sulfonic acids, eg. ligno-,phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fattyacids, alkyl- and alkylaryl sulfonates, alkyl, lauryl ether and fattyalcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanolsor of fatty alcohol glycol ethers, condensates of sulfonated naphthaleneand its derivatives with formaldehyde, condensates of naphthalene or ofthe naphthalenesulfonic acids with phenol and formaldehyde,polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- ornonylphenol, alkylphenol [sic] or tributylphenyl polyglycol ether,alkylaryl polyether alcohols, isotridecyl alcohol, fattyalcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers or polyoxypropylene [sic], lauryl alcoholpolyglycol ether acetate, sorbitol esters, lignosulfite waste liquors ormethylcellulose.

Powders, materials for spreading and dusts can be prepared by mixing orjointly grinding the compounds I or II, or I or III, or the mixture ofthe compounds I and II, or I and III, with a solid carrier.

Granules (eg. coated granules, impregnated granules or homogeneousgranules) are usually prepared by binding the active ingredient, oractive ingredients, to a solid carrier.

Fillers or solid carriers are, for example, mineral earths such assilica gel, silicas, silica gels [sic], silicates, talc, kaolin,limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth,calcium sulfate, magnesium sulfate, magnesium oxide, ground syntheticmaterials, and fertilizers, such as ammonium sulfate, ammoniumphosphate, ammonium nitrate, ureas, and products of vegetable origin,such as cereal meal, tree bark meal, wood meal and nutshell meal,cellulose powders or other solid carriers.

The formulations generally comprise 0.1 to 95% by weight, preferably 0.5to 90% by weight, of one of the compounds I or II, or I or III, or ofthe mixture of the compounds I and II, or I and III. The activeingredients are employed in a purity of from 90% to 100%, preferably 95%to 100% (according to NMR or HPLC spectrum [sic]).

The compounds I or II, or I or III, or the mixtures or the correspondingformulations, are applied by treating the harmful fungi or the plants,seeds, soils, areas, materials or spaces to be kept free from them witha fungicidally active amount of the mixture, or of the compounds I andII, or I and III in the case of separate application. Application can beeffected before or after infection by the harmful fungi.

Examples of the synergistic action of the mixtures according to theinvention against harmful fungi

The fungicidal action of the compounds and of the mixtures wasdemonstrated by the following experiments:

The active ingredients, separately or together, were prepared as a 10%emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weightof Nekanil® LN (Lutensol® AP6, wetting agents having emulsifying anddispersing action, based on ethoxylated alkylphenols) and 10% by weightof Emulphor® EL (Emulan® EL, emulsifier based on ethoxylated fattyalcohols) and diluted with water to give the desired concentration.

Evaluation was by determining the infected leaf areas in percent. Thesepercentages were converted into efficacies. The expected efficacies ofthe mixtures of the active ingredients were determined using Colby'sformula [R. S. Colby, Weeds 15, 20-22 (1967)] and compared with theobserved efficacies. colby's formula:

    E=x+y-x·y/100

E expected efficacy, expressed in % of the untreated control, when usingthe mixture of the active ingredients A and B at the concentrations aand b

x efficacy, expressed in % of the untreated control, when using activeingredient A at a concentration of a

y efficacy, expressed in % of the untreated control, when using activeingredient B at a concentration of b

An efficacy of 0 means that the infection level of the treated plantscorresponds to that of the untreated control plants; an efficacy of 100means thats the treated plants were not infected.

Activity against Botrytis cinerea (gray mold)

Bellpepper seedings (cultivar: "Neusiedler Ideal Elite") having 4-5leaves were sprayed to runoff point with the preparation of the activeingredient. After the plants had dried, they were sprayed with a conidiasuspension of the fungus Botrytis cinerea and kept for 5 days at 22-24°C. and high atmospheric humidity. The test was evaluated visually.

The test results are complied in the tables which follow:

Activity of the active ingredients when applied separately:

    ______________________________________                                                        Rate of                                                          application                                                                  Active ingredient [ppm] Efficacy [%]                                        ______________________________________                                        I.1 (R = H)     200       36                                                     125 36                                                                        100 49                                                                        50 36                                                                        I.2 (R = F) 200 61                                                             125 36                                                                        100 49                                                                        50 10                                                                        II (Captan) 100  0                                                             50 23                                                                         25  0                                                                         12.5 10                                                                      III (Folpet) 100 36                                                            50 23                                                                         25 10                                                                         12.5  0                                                                      untreated control --/--  0                                                  ______________________________________                                    

    ______________________________________                                        Synergistic mixture                                                           Active                   Efficacy                                             ingredients                                                                             ppm       Ratio    observed                                                                             calculated                                ______________________________________                                        I.1 + II  125 + 12.5                                                                              10/1     87     42                                           200 + 200  1/1 94 50                                                          100 + 100  1/1 87 49                                                          50 + 50  1/1 81 50                                                           I.1 + III 125 + 12.5 10/1  87 36                                               200 + 200  1/1 87 50                                                          100 + 100  1/1 91 67                                                          50 + 50  1/1 87 50                                                           I.2 + II  125 + 12.5 10/1  87 65                                               200 + 200  1/1 74 50                                                          100 + 100  1/1 81 49                                                          50 + 50  1/1 81 31                                                           I.2 + III 125 + 12.5 10/1  74 61                                               200 + 200  1/1 81 50                                                          100 + 100  1/1 94 67                                                          50 + 50  1/1 96 31                                                         ______________________________________                                    

We claim:
 1. A fungicidal composition comprisinga) an oxime ethercarboxamide compound of the formula I ##STR5## where R is hydrogen orhalogen, and b) a phthalimide selected from the group consisting of thecompounds II and III ##STR6## in a synergistically active amount.
 2. Thefungicidal composition defined in claim 1, comprising the phthalimidecompound II.
 3. The fungicidal composition defined in claim 1,comprising the phthalimide compound III.
 4. The fungicidal compositiondefined in claim 1, wherein the weight ratio of the compound of theformula I to the compound II or the compound III is 1:1 to 1:100.
 5. Amethod of controlling harmful fungi, which comprises treating theharmful fungi, their environment, or the plants, seeds, soils, areas,materials or spaces to be kept free from said fungi with asynergistically effective amount of the compound of the formula I asdefined in claim 1 and the compound II as defined in claim 1 or thecompound III as defined in claim
 1. 6. The method defined in claim 5,wherein the compound of the formula I and the compound II or thecompound III are applied simultaneously together or separately, or insuccession.
 7. The method defined in claim 5, wherein from 0.005 to 0.5kg/ha of the compound of the formula I are applied.
 8. The methoddefined in claim 5, wherein from 0.1 to 5 kg/ha of the compound II orthe compound III are applied.